(η(5)-pentamethyl-cyclopentadienyl)W(S)(S2)Cl | 365439-41-4

• 英文名称: (η(5)-pentamethyl-cyclopentadienyl)W(S)(S2)Cl
• CAS: 365439-41-4
• 化学式: C₁₀H₁₅ClS₃W
• 分子量: 450.73
• InChiKey: NTWFTIJPPSVAOP-UHFFFAOYSA-M

反应信息

• 作为反应物：
  描述：

  (η(5)-pentamethyl-cyclopentadienyl)W(S)(S2)Cl 、 氧气 生成 (η(5)-pentamethyl-cyclopentadienyl)W(O)(S2)Cl
  参考文献：
  名称：

  Chalkogen-Derivate der Halbsandwich-Wolfram(V)-Komplexe Cp*WCl4 und Cp*WCl4(PMe3). Röntgen-Kristallstrukturanalysen vonanti-[Cp*W(Se)(μ-Se)]2 und Cp*W(S)2(OMe)

  摘要：

  The chalcogenation Of CP*WCl4 (1) by E(SiMe3)(2) (E = S, Se) and Te((SiMe2Bu)-Bu-t)2 in chloroform solution leads to dimeric products of the type anti-[Cp*W(E)(mu -E)](2) (E = S (3a), Se (3b) and Te (3c)). An X-ray structure determination of 3b indicates a centrosymmetric molecule containing a planar W(mu -Se)(2)W ring, the W-W distance (297.9(1) pm) corresponds to a single bond. In the presence of air the two terminal chalcogenido ligands (E) in 3a-c are stepwise replaced by oxido ligands (O) to give [CP*W(O)(mu -E)](2) (E = S (5a), Se (5b) and Te (5c)) in quantitative yields.The reaction Of CP*WCl4 with H2S or ammonium polysulfide, (NH4)(2)S-x (x similar to 10), leads to Cp*W(S)(2)Cl (6a); the corresponding methoxy derivative, CP*W(S)(2)OCH3 (9a), has been characterized by an X-ray structure analysis. On the other hand, the reaction Of Cp*WCl4(PMe3) (2) with sodium tetrasulfide, Na2S4, in dimethylformamide solution gives a mixture of mononuclear Cp*W(S)(S-2)Cl (8a), dinuclear [Cp*W(S)(mu -S)](2) (3a) and a trinuclear side-product of composition Cp*W3S7 (13a). Terminal sulfido ligands are replaced by terminal oxido ligands in solution in the presence of oxygen. Thus, 6a is stepwise converted into Cp*W(O)(S)Cl (10a) and CpW(O)(2)Cl (12a), whereas 8a gives CP*W(O)(S-2)Cl (11a) and 13a leads to Cp*W-3(O)S-6 (14a). The disulfido complexes 8a and 11a are desulfurized by triphenylphosphane to give 6a and 10a. The new complexes have been characterized by their IR and NMR spectra and by mass spectrometry.

  DOI：

  10.1002/1521-3749(200108)627:8<1759::aid-zaac1759>3.0.co;2-v
• 作为产物：
  描述：

  diboron trisulfide 、 (η(5)-pentamethyl-cyclopentadienyl)W(O)(S2)Cl 生成 (η(5)-pentamethyl-cyclopentadienyl)W(S)(S2)Cl
  参考文献：
  名称：

  Chalkogen-Derivate der Halbsandwich-Wolfram(V)-Komplexe Cp*WCl4 und Cp*WCl4(PMe3). Röntgen-Kristallstrukturanalysen vonanti-[Cp*W(Se)(μ-Se)]2 und Cp*W(S)2(OMe)

  摘要：

  The chalcogenation Of CP*WCl4 (1) by E(SiMe3)(2) (E = S, Se) and Te((SiMe2Bu)-Bu-t)2 in chloroform solution leads to dimeric products of the type anti-[Cp*W(E)(mu -E)](2) (E = S (3a), Se (3b) and Te (3c)). An X-ray structure determination of 3b indicates a centrosymmetric molecule containing a planar W(mu -Se)(2)W ring, the W-W distance (297.9(1) pm) corresponds to a single bond. In the presence of air the two terminal chalcogenido ligands (E) in 3a-c are stepwise replaced by oxido ligands (O) to give [CP*W(O)(mu -E)](2) (E = S (5a), Se (5b) and Te (5c)) in quantitative yields.The reaction Of CP*WCl4 with H2S or ammonium polysulfide, (NH4)(2)S-x (x similar to 10), leads to Cp*W(S)(2)Cl (6a); the corresponding methoxy derivative, CP*W(S)(2)OCH3 (9a), has been characterized by an X-ray structure analysis. On the other hand, the reaction Of Cp*WCl4(PMe3) (2) with sodium tetrasulfide, Na2S4, in dimethylformamide solution gives a mixture of mononuclear Cp*W(S)(S-2)Cl (8a), dinuclear [Cp*W(S)(mu -S)](2) (3a) and a trinuclear side-product of composition Cp*W3S7 (13a). Terminal sulfido ligands are replaced by terminal oxido ligands in solution in the presence of oxygen. Thus, 6a is stepwise converted into Cp*W(O)(S)Cl (10a) and CpW(O)(2)Cl (12a), whereas 8a gives CP*W(O)(S-2)Cl (11a) and 13a leads to Cp*W-3(O)S-6 (14a). The disulfido complexes 8a and 11a are desulfurized by triphenylphosphane to give 6a and 10a. The new complexes have been characterized by their IR and NMR spectra and by mass spectrometry.

  DOI：

  10.1002/1521-3749(200108)627:8<1759::aid-zaac1759>3.0.co;2-v